Synthesis method of tomato leaf miner sex pheromone compound

Abstract

The invention discloses a synthesis method of a sex pheromone compound of phyllocnistis citrella, which specifically comprises the following steps: generating corresponding quaternary phosphonium salt by using cis-3-hexenol as an initial raw material through bromination reaction, then generating cis-4-cis-7-decadienol through witting reaction, and synthesizing (3E, 8Z, 8Z, 8Z)-1, 2, 3-triazole-3-one through multi-step reaction such as coupling and trans-hydrogenation. (3E, 8Z, 11Z)-tetradecatriene alcohol is subjected to an esterification reaction through pyridine / acetic anhydride, and (3E, 8Z, 11Z)-tetradecatriene acetate is generated. The method has the advantages of cheap and easily available raw materials, simple and reasonable synthesis steps, mild reaction conditions, convenience in operation and ideal yield.

Description

Technical Field

[0001] The invention relates to the technical field of agricultural pest control, and more particularly to a method for synthesizing a sex pheromone compound of tomato leafminer. Background Art

[0002] Tuta absoluta (Meyrick), a major global quarantine pest that harms Solanaceae crops, originated in South America and has since spread to Asia, Europe, and Africa at an extremely fast rate. By 2017, it had invaded about 90 countries around the world, including seven of the top ten tomato-growing countries (India, Turkey, Egypt, Italy, Iran, Spain, and Brazil), and the area of ​​tomatoes it harms accounts for more than half of the world's tomato-growing area. In severe cases, it can lead to a near total loss of tomato crops in the invaded areas.

[0003] my country is the world's largest producer of tomatoes, and the pest has now invaded Xinjiang and Yunnan, seriously affecting the safety of the local agricultural industry and posing a huge potential threat to other tomato and potato producing areas in my country. It has a wide range of hosts, harming nearly 40 plant species in nine families, including the Solanaceae family. The insect has strong adaptability to the environment, with 10 to 12 generations per year, and the larvae burrow into the host plant tissue to feed on the mesophyll.

[0004] At present, the means of controlling tomato armyworm mainly rely on pesticide control, such as emamectin benzoate, emamectin benzoate and indoxacarb, high-efficiency chlorfenapyr, rotenone, and ethoxyfen. However, although the long-term and uncontrolled use of chemical pesticides has a certain killing effect on pests, the application of pesticides will also cause killing to their natural enemies, destroy the ecological balance, and cause a large degree of environmental pollution and pesticide residues in fruits, which will cause irreversible damage to nature and humans. The long-term and repeated use of chemical pesticides will also cause pests to develop resistance to conventional pesticides, so that pests continue to occur on a large scale.

[0005] Chemical pheromone technology is an emerging green pest control technology in the world. It has the advantages of high specificity, low risk and environmental friendliness, and has a wide range of application value in China. Insect pheromones are in line with the path of green ecological agriculture because of their strong specificity, high efficiency, no harm to other organisms, non-toxicity and no pollution.

[0006] Therefore, how to synthesize an efficient, simple and feasible tomato armyworm sex pheromone compound is an urgent problem to be solved by technicians in this field. Summary of the invention

[0007] In view of this, the object of the present invention is to provide a method for synthesizing a sex pheromone compound of tomato leafminer to solve the deficiencies in the prior art.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] A method for synthesizing a sex pheromone compound of a tomato leafminer comprises the following steps:

[0010] (1) dissolving triphenylphosphine and N-bromosuccinimide in anhydrous dichloromethane, cooling, adding cis-3-hexenol (Compound 1) under argon protection, stirring until the reaction is complete, washing, quenching the reaction with saturated sodium carbonate solution, removing dichloromethane from the reaction solution under reduced pressure, dissolving the residue in ether, combining the ether solution, washing with saturated sodium carbonate solution, saturated ammonium chloride solution and saturated brine in sequence, drying over anhydrous magnesium sulfate, concentrating, and purifying by column chromatography to obtain (cis)-1-bromo-3-hexene (Compound 2);

[0011] (2) dissolving (cis)-1-bromo-3-hexene in anhydrous toluene, adding triphenylphosphine, reacting, filtering to obtain a white solid, crystallizing the product with acetonitrile, and drying in a vacuum to obtain (cis)-3-hexenetriphenylphosphonium bromide (compound 3);

[0012] (3) Dissolve (cis)-3-hexenyltriphenylphosphonium bromide in anhydrous tetrahydrofuran, add sodium hydride, stir, react, cool, dropwise add 4-acetoxybutyraldehyde in tetrahydrofuran, stir until complete reaction, add saturated ammonium chloride solution to quench the reaction, add ether to extract, wash with saturated ammonium chloride solution and saturated brine in sequence, dry over anhydrous sodium sulfate, filter, concentrate, and purify the crude product by column chromatography to obtain cis-4-cis-7-decadienol acetate (Compound 4);

[0013] (4) dissolving cis-4-cis-7-decadienol acetate in methanol, adding lithium hydroxide, stirring until the reaction is complete, removing methanol by distillation under reduced pressure, adding ether for extraction, washing with saturated ammonium chloride solution and saturated brine in sequence, drying over anhydrous sodium sulfate, filtering, and concentrating to obtain cis-4-cis-7-decadienol (compound 5);

[0014] (5) Dissolve triphenylphosphine and N-bromosuccinimide in anhydrous dichloromethane, cool, add cis-4-cis-7-decadienol under argon protection, stir until the reaction is complete, wash, quench the reaction with saturated sodium carbonate solution, remove dichloromethane from the reaction solution under reduced pressure, dissolve the residue in ether, combine the ether solutions, wash with saturated sodium carbonate solution, saturated ammonium chloride solution and saturated brine in sequence, dry over anhydrous magnesium sulfate, concentrate, and purify by column chromatography to obtain 1-bromo-cis-4-cis-7-decadiene (Compound 6);

[0015] (6) Under argon protection, 3-butyne-1-ol pyranyl ether was dissolved in anhydrous tetrahydrofuran, cooled, n-butyl lithium solution was added dropwise, the temperature was raised, the reaction was continued, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidone (DMPU) was added dropwise, the reaction solution was stirred, the reaction solution was cooled again, 1-bromo-cis-4-cis-7-decadiene tetrahydrofuran solution was added dropwise, the temperature was raised to room temperature again, the reaction was continued, and a saturated aqueous ammonium chloride solution was used to quench the reaction, the organic phase was separated, the aqueous phase was extracted with ether, the organic phases were combined, washed with distilled water and saturated brine in turn, dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was subjected to column chromatography to obtain cis-8-cis-11-tetradecene-3-yn-1-ol pyranyl ether (Compound 7);

[0016] (7) dissolving lithium aluminum hydride in diethyl ether, adding dropwise compound 7 cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether diluted with diethyl ether, reacting, adding ethyl acetate to quench the reaction after the reaction is completed, adding dropwise water, and then adding sodium hydroxide solution until it is clear, separating the liquids, washing with distilled water and saturated brine in turn, drying with anhydrous sodium sulfate, and subjecting the crude product to column chromatography to obtain trans-3-cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether (compound 8);

[0017] (8) Dissolve trans-3-cis-8-cis-11-tetradecatrienol pyranyl ether in methanol, add p-toluenesulfonic acid, stir until the reaction is complete, quench the reaction with a saturated sodium bicarbonate solution, remove methanol under reduced pressure, dissolve the residue in ethyl acetate, wash with a saturated sodium bicarbonate solution and a saturated saline solution in sequence, dry over anhydrous magnesium sulfate, filter, concentrate, and purify the crude product by column chromatography to obtain trans-3-cis-8-cis-11-tetradecatrienol (Compound 9);

[0018] (9) Dissolve trans-3-cis-8-cis-11-tetradecatrienol in pyridine, cool, add acetic anhydride dropwise, and stir until the reaction is complete. After the reaction is completed, add saturated ammonium chloride solution to quench the reaction, extract with ether, wash with hydrochloric acid solution, separate the layers, wash with sodium bicarbonate solution and saturated brine in sequence, dry with anhydrous sodium sulfate, filter, and concentrate. The crude product is purified by column chromatography to obtain trans-3-cis-8-cis-11-tetradecatrienyl acetate (Compound 10), which is the sex pheromone compound of the tomato leafminer.

[0019] The present invention uses cis-3-hexenol as a starting material, generates a corresponding quaternary phosphonium salt through a bromination reaction, generates cis-4-cis-7-decadienol through a witting reaction, and then synthesizes (3E, 8Z, 11Z)-tetradecatrienol through multiple steps of reactions such as coupling and trans-hydrogenation, and then generates (3E, 8Z, 11Z)-tetradecatrienol through an esterification reaction with pyridine / acetic anhydride. The chemical formula is:

[0020]

[0021] Furthermore, in the above step (1), the usage ratio of triphenylphosphine, N-bromosuccinimide, dichloromethane and cis-3-hexenol is 1.2 mol:1.2 mol:1500 mL:1.05 mol; and the mixture is cooled to -30°C.

[0022] Furthermore, in the above step (2), the usage ratio of (cis)-1-bromo-3-hexene, toluene and triphenylphosphine is 0.7 mol:1000 mL:0.84 mol; the reaction temperature is 90°C and the reaction time is 12 h; and the vacuum drying temperature is 50°C.

[0023] Furthermore, in the above step (3), the ratio of (cis)-3-hexenetriphenylphosphonium bromide, tetrahydrofuran solution and sodium hydride is 0.6 mol:800 mL:17.3 g; the reaction time is 4 h; and the mixture is cooled to -20°C.

[0024] Furthermore, in the above step (4), the usage ratio of cis-4-cis-7-decadienol acetate, methanol and lithium hydroxide is 0.3 mol:300 mL:0.36 mol.

[0025] Furthermore, in the above step (5), the usage ratio of triphenylphosphine, N-bromosuccinimide, dichloromethane and cis-4-cis-7-decadienol is 0.31 mol:0.31 mol:500 mL:0.26 mol; and the mixture is cooled to -30°C.

[0026] Furthermore, in the above step (6), the amount ratio of 3-butyn-1-ol pyranyl ether, anhydrous tetrahydrofuran, n-butyl lithium solution, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidone and 1-bromo-cis-4-cis-7-decadiene is 0.2 mol:400 mL:0.3 mol:0.56 mol:0.15 mol; cooling to -20°C; the solvent of the n-butyl lithium solution is 2.5 mol / L n-hexane solution; heating to 0°C; reaction time is 3 to 4 h; stirring time is 2 h; cooling to -78°C again; heating to room temperature again, heating time is 8 h; and continuing reaction time is 12 h.

[0027] Furthermore, in the above step (7), the usage ratio of lithium aluminum hydride, diethyl ether, cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether and water is 0.5 mol:200 mL:0.1 mol:50 mL; and the mass concentration of the sodium hydroxide solution is 10%.

[0028] Furthermore, in the above step (8), the ratio of trans-3-cis-8-cis-11-tetradecatrienol pyranyl ether, methanol and p-toluenesulfonic acid is 0.06 mol:250 mL:6 mmol.

[0029] Furthermore, in the above step (9), the ratio of trans-3-cis-8-cis-11-tetradecatrienol, pyridine and acetic anhydride is 0.04 mol:100 mL:0.048 mol; the mixture is cooled to 0° C.; and the mass concentration of the hydrochloric acid solution is 10%.

[0030] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] The raw materials of the invention are cheap and easily available, the synthesis steps are simple and reasonable, the reaction conditions are mild, the operation is convenient and the yield is ideal. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is the mass spectrometer of trans-3-cis-8-cis-11-tetradecatriene acetate of Example 1. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] The method for synthesizing the sex pheromone compound of tomato leafminer specifically comprises the following steps:

[0036] (1) In a dry 3L flask, triphenylphosphine (314.4 g, 1.2 mol) and N-bromosuccinimide (213.6 g, 1.2 mol) were dissolved in 1500 mL of anhydrous dichloromethane, cooled to -30°C, and cis-3-hexenol (105 g, 1.05 mol) was added under argon protection, stirred until the reaction was complete (TLC detection), washed, and quenched with saturated sodium carbonate solution. The dichloromethane was removed from the reaction solution under reduced pressure, and the residue was dissolved in ether. The ether solution was combined and washed with saturated sodium carbonate solution, saturated ammonium chloride solution and saturated brine in sequence, dried over anhydrous magnesium sulfate, concentrated, and purified by column chromatography to obtain (cis)-1-bromo-3-hexene as a light yellow liquid weighing 139 g;

[0037] (2) In a dry 2L flask, (cis)-1-bromo-3-hexene (114.1 g, 0.7 mol) was dissolved in 1000 mL of anhydrous toluene, triphenylphosphine (221. g, 0.84 mol) was added, and the mixture was reacted at 90°C for 12 h. A white solid was obtained by filtration. The product was crystallized with acetonitrile and dried under vacuum at 50°C to obtain (cis)-3-hexenetriphenylphosphonium bromide, weighing 288 g.

[0038] (3) In a dry 2L three-necked flask, (cis)-3-hexene triphenylphosphonium bromide (237 g, 0.6 mol) was dissolved in 800 mL of anhydrous tetrahydrofuran, 17.3 g of sodium hydride was added, and the mixture was stirred. The reaction flask was connected to a gas bubbler, and a red solution was obtained after 4 h of reaction. The mixture was cooled to -20°C, and a tetrahydrofuran solution of 4-acetoxybutyraldehyde was added dropwise. The mixture was stirred until the reaction was complete (TLC detection). A saturated ammonium chloride solution was added to quench the reaction, and ether was added for extraction. The mixture was washed with a saturated ammonium chloride solution and a saturated saline solution in turn, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by column chromatography to obtain cis-4-cis-7-decadienol acetate as a light yellow transparent liquid weighing 79 g.

[0039] (4) In a dry 1L three-necked flask, cis-4-cis-7-decadienol acetate (58.9 g, 0.3 mol) was dissolved in 300 mL of methanol, lithium hydroxide (8.6 g, 0.36 mol) was added, and the mixture was stirred until the reaction was complete (TLC detection), and the methanol was removed by distillation under reduced pressure. Ether was added for extraction, and the mixture was washed with saturated ammonium chloride solution and saturated brine in sequence, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain cis-4-cis-7-decadienol as a colorless transparent liquid weighing 42.6 g;

[0040] (5) In a dry 2L flask, triphenylphosphine (81.2 g, 0.31 mol) and N-bromosuccinimide (55.18 g, 0.31 mol) were dissolved in 500 mL of anhydrous dichloromethane, cooled to -30°C, and cis-4-cis-7-decadienol (40 g, 0.26 mol) was added under argon protection, stirred until the reaction was complete (TLC detection), washed, and quenched with saturated sodium carbonate solution. The dichloromethane was removed from the reaction solution under reduced pressure, and the residue was dissolved in ether. The ether solution was combined and washed with saturated sodium carbonate solution, saturated ammonium chloride solution and saturated brine in sequence, dried over anhydrous magnesium sulfate, concentrated, and purified by column chromatography to obtain 1-bromo-cis-4-cis-7-decadiene as a light yellow liquid weighing 35.9 g;

[0041] (6) Under argon protection, 3-butyn-1-ol pyranyl ether (29.8 g, 0.2 mol) was dissolved in 400 mL of anhydrous tetrahydrofuran, cooled to -20°C, n-butyl lithium solution (118 mL, 0.3 mol, 2.5 mol / L n-hexane solution) was added dropwise, the temperature was raised to 0°C, the reaction was continued for 4 h, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone (68 mL, 0.56 mol) was added dropwise, the reaction mixture was stirred for 2 h, the reaction solution was cooled to -78°C, 1 -bromo-cis-4-cis-7-decadiene (32.6 g, 0.15 mol) in tetrahydrofuran, warmed to room temperature within 8 h, continued to react for 12 h, quenched the reaction with saturated ammonium chloride aqueous solution, separated the organic phase, extracted the aqueous phase with ether, combined the organic phases, washed with distilled water and saturated brine in turn, dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was subjected to column chromatography to obtain cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether, a colorless transparent liquid weighing 38.6 g;

[0042] (7) In a 500 mL three-necked flask, lithium aluminum hydride (1.9 g, 0.5 mol) was dissolved in 200 mL of ether, and compound 7 cis-8-cis-11-tetradecene-3-yn-1-ol pyranyl ether (28.5 g, 0.1 mol) diluted with ether was added dropwise. The reaction was monitored by GC. After the reaction was completed, ethyl acetate was added to quench the reaction, 50 mL of water was added dropwise, and then 10% sodium hydroxide solution was added until it was clear. The liquid was separated, and the mixture was washed with distilled water and saturated brine in turn, and dried over anhydrous sodium sulfate. The crude product was subjected to column chromatography to obtain trans-3-cis-8-cis-11-tetradecene-3-yn-1-ol pyranyl ether, a colorless transparent liquid weighing 18.2 g.

[0043] (8) In a 500 mL three-necked flask, trans-3-cis-8-cis-11-tetradecatrienol pyranyl ether (17.2 g, 0.06 mol) was dissolved in 250 mL of methanol, p-toluenesulfonic acid (1.1 g, 6 mmol) was added, and the mixture was stirred at room temperature until the reaction was complete (TLC detection). The reaction was quenched with a saturated sodium bicarbonate solution, and the methanol was removed under reduced pressure. The residue was dissolved in ethyl acetate, washed with a saturated sodium bicarbonate solution and a saturated saline solution in sequence, dried over anhydrous magnesium sulfate, filtered, concentrated, and the crude product was purified by column chromatography to obtain trans-3-cis-8-cis-11-tetradecatrienol as a colorless transparent liquid weighing 12 g;

[0044] (9) Dissolve trans-3-cis-8-cis-11-tetradecatrienol (8.3 g, 0.04 mol) in 100 mL of pyridine, cool to 0°C, add acetic anhydride (4.8 g, 0.048 mol) dropwise, and stir until the reaction is complete (TLC detection). After the reaction is completed, add saturated ammonium chloride solution to quench the reaction, extract with ether, wash with 10% hydrochloric acid solution, separate the liquids, wash with sodium bicarbonate solution and saturated brine in turn, dry with anhydrous sodium sulfate, filter, concentrate, and purify the crude product by column chromatography to obtain trans-3-cis-8-cis-11-tetradecatrienyl acetate, a colorless transparent liquid weighing 8.6 g, which is the sex pheromone compound of the tomato leafminer.

[0045] Performance Testing

[0046] 1. Yield calculation

[0047] The calculated yields of the products in steps (1) to (9) of Example 1 are shown in Table 1 below.

[0048] Table 1 Yields of the products in steps (1)-(9) of Example 1

[0049]

[0050] As shown in Table 1, the total yield of trans-3-cis-8-cis-11-tetradecatriene acetate in the present invention is 13.8% with cis-3-hexenol as the raw material after 9 steps of reaction.

[0051] 2. Gas Spectrum

[0052] Example 1 The mass spectrometer of trans-3-cis-8-cis-11-tetradecatriene acetate is as follows Figure 1 shown.

[0053] Depend on Figure 1 It can be seen that according to the molecular formula of trans-3-cis-8-cis-11-tetradecatriene acetate, C 16 H 26 O2, molecular weight is 250, Figure 1 Corresponding to 250 in the spectrum, it is inferred that the synthetic structure of the product is correct.

[0054] 3. Field moth trapping test

[0055] Take the trans-3-cis-8-cis-10-tetradecatriene acetate of Example 1 and prepare it into a tomato armyworm lure. In March and April 2024, a field moth-attracting effect comparison test was conducted in a test field in Xichang City, Sichuan Province. The number of Spodoptera litura trapped by 6 groups of tomato armyworm lures 5 times (each time with an interval of 2-3 days) was counted, and the average value was calculated.

[0056] The results are shown in Table 2.

[0057] Table 2 Comparative test results of moth-attracting effect in the field

[0058] Tomato armyworm bait March 28 March 30 April 2 April 4 April 7 1 215 93 204 61 58 2 79 113 94 52 50 3 135 131 88 38 25 4 15 80 145 66 44 5 125 131 28 135 135 6 121 150 25 15 88 average value 115 116 97 61 67

[0059] It can be seen from Table 2 that the trans-3-cis-8-cis-10-tetradecatriene acetate in Example 1 has a better insect attracting effect.

[0060] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for synthesizing a sex pheromone compound of tomato leafminer, characterized in that: The specific steps include: (1) dissolving triphenylphosphine and N-bromosuccinimide in anhydrous dichloromethane, cooling, adding cis-3-hexenol under argon protection, stirring until the reaction is complete, washing, quenching the reaction with a saturated sodium carbonate solution, removing dichloromethane from the reaction solution under reduced pressure, dissolving the residue in ether, combining the ether solutions, washing with a saturated sodium carbonate solution, a saturated ammonium chloride solution and a saturated saline solution in sequence, drying over anhydrous magnesium sulfate, concentrating, and purifying by column chromatography to obtain (cis)-1-bromo-3-hexene; (2) dissolving (cis)-1-bromo-3-hexene in anhydrous toluene, adding triphenylphosphine, reacting, filtering to obtain a white solid, crystallizing the product with acetonitrile, and drying in vacuum to obtain (cis)-3-hexenetriphenylphosphonium bromide; (3) dissolving (cis)-3-hexenyltriphenylphosphonium bromide in anhydrous tetrahydrofuran, adding sodium hydride, stirring, reacting, cooling, adding dropwise a tetrahydrofuran solution of 4-acetoxybutyraldehyde, stirring until the reaction is complete, adding a saturated ammonium chloride solution to quench the reaction, adding ether for extraction, washing with a saturated ammonium chloride solution and a saturated saline solution in sequence, drying over anhydrous sodium sulfate, filtering, concentrating, and purifying the crude product by column chromatography to obtain cis-4-cis-7-decadienol acetate; (4) dissolving cis-4-cis-7-decadienol acetate in methanol, adding lithium hydroxide, stirring until the reaction is complete, removing methanol by distillation under reduced pressure, adding ether for extraction, washing with saturated ammonium chloride solution and saturated brine in sequence, drying over anhydrous sodium sulfate, filtering, and concentrating to obtain cis-4-cis-7-decadienol; (5) dissolving triphenylphosphine and N-bromosuccinimide in anhydrous dichloromethane, cooling, adding cis-4-cis-7-decadienol under argon protection, stirring until the reaction is complete, washing, quenching the reaction with saturated sodium carbonate solution, removing dichloromethane from the reaction solution under reduced pressure, dissolving the residue in ether, combining the ether solutions, washing with saturated sodium carbonate solution, saturated ammonium chloride solution and saturated brine in sequence, drying over anhydrous magnesium sulfate, concentrating, and purifying by column chromatography to obtain 1-bromo-cis-4-cis-7-decadiene; (6) Under argon protection, 3-butyne-1-ol pyranyl ether was dissolved in anhydrous tetrahydrofuran, cooled, n-butyl lithium solution was added dropwise, the temperature was raised, the reaction was carried out, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidone was added dropwise, the reaction solution was stirred, the reaction solution was cooled again, 1-bromo-cis-4-cis-7-decadiene tetrahydrofuran solution was added dropwise, the temperature was raised to room temperature again, the reaction was continued, and a saturated aqueous ammonium chloride solution was used to quench the reaction, the organic phase was separated, the aqueous phase was extracted with ether, the organic phases were combined, washed with distilled water and saturated brine in turn, dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was subjected to column chromatography to obtain cis-8-cis-11-tetradecene-3-yn-1-ol pyranyl ether; (7) dissolving lithium aluminum hydride in diethyl ether, adding dropwise compound 7 cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether diluted with diethyl ether, reacting, adding ethyl acetate to quench the reaction after the reaction is completed, adding dropwise water, and then adding sodium hydroxide solution until it is clear, separating the liquids, washing with distilled water and saturated brine in turn, drying with anhydrous sodium sulfate, and subjecting the crude product to column chromatography to obtain trans-3-cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether; (8) dissolving trans-3-cis-8-cis-11-tetradecatrienol pyranyl ether in methanol, adding p-toluenesulfonic acid, stirring until the reaction is complete, quenching the reaction with a saturated sodium bicarbonate solution, removing methanol under reduced pressure, dissolving the residue in ethyl acetate, washing with a saturated sodium bicarbonate solution and a saturated saline solution in sequence, drying over anhydrous magnesium sulfate, filtering, concentrating, and purifying the crude product by column chromatography to obtain trans-3-cis-8-cis-11-tetradecatrienol; (9) Dissolve trans-3-cis-8-cis-11-tetradecatrienol in pyridine, cool, add acetic anhydride dropwise, and stir until the reaction is complete. After the reaction is completed, add saturated ammonium chloride solution to quench the reaction, extract with ether, wash with hydrochloric acid solution, separate the liquids, wash with sodium bicarbonate solution and saturated brine in turn, dry with anhydrous sodium sulfate, filter, concentrate, and purify the crude product by column chromatography to obtain trans-3-cis-8-cis-11-tetradecatrienyl acetate, which is the tomato leafminer sex pheromone compound.

2. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (1), the ratio of triphenylphosphine, N-bromosuccinimide, dichloromethane and cis-3-hexenol is 1.2 mol:1.2 mol:1500 mL:1.05 mol; and the cooling is to -30°C.

3. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (2), the amount ratio of (cis)-1-bromo-3-hexene, toluene and triphenylphosphine is 0.7 mol:1000 mL:0.84 mol; the reaction temperature is 90° C. and the reaction time is 12 h; and the vacuum drying temperature is 50° C.

4. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (3), the amount ratio of (cis)-3-hexenetriphenylphosphonium bromide, tetrahydrofuran solution and sodium hydride is 0.6 mol:800 mL:17.3 g; the reaction time is 4 h; and the cooling is to -20°C.

5. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (4), the usage ratio of cis-4-cis-7-decadienol acetate, methanol and lithium hydroxide is 0.3 mol:300 mL:0.36 mol.

6. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (5), the ratio of triphenylphosphine, N-bromosuccinimide, dichloromethane and cis-4-cis-7-decadienol is 0.31 mol:0.31 mol:500 mL:0.26 mol; and the cooling is to -30°C.

7. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (6), the amount ratio of the 3-butyn-1-ol pyranyl ether, anhydrous tetrahydrofuran, n-butyl lithium solution, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidone and 1-bromo-cis-4-cis-7-decadiene is 0.2 mol:400 mL:0.3 mol:0.56 mol:0.15 mol; the cooling to -20°C; the solvent of the n-butyl lithium solution is 2.5 mol / L n-hexane solution; the heating to 0°C; the reaction time is 3 to 4 h; the stirring time is 2 h; the cooling to -78°C again; the heating to room temperature again, the heating time is 8 h; the continued reaction time is 12 h.

8. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (7), the amount ratio of lithium aluminum hydride, ether, cis-8-cis-11-tetradecene-3-yn-1-ol pyran ether and water is 0.5 mol:200 mL:0.1 mol:50 mL; and the mass concentration of the sodium hydroxide solution is 10%.

9. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (8), the amount ratio of the trans-3-cis-8-cis-11-tetradecatrienol pyranyl ether, methanol and p-toluenesulfonic acid is 0.06 mol: 250 mL: 6 mmol.

10. The method for synthesizing a sex pheromone compound of tomato leafminer according to claim 1, characterized in that: In step (9), the ratio of the amount of trans-3-cis-8-cis-11-tetradecatrienol, pyridine and acetic anhydride is 0.04 mol:100 mL:0.048 mol; the cooling is to 0° C.; and the mass concentration of the hydrochloric acid solution is 10%.

Images